DE10313317A1 - Water-dispersed powder slurry coating contains a particulate material containing a resin with active hydrogen and a reactive surfactant with an optionally blocked isocyanate group and an epoxide group - Google Patents

Abstract

A water-dispersed powder slurry coating includes (a) a particulate material containing a resin with active hydrogen; (b) a reactive surfactant with an optionally blocked isocyanate group and an epoxide group; and (c) an aqueous medium containing (A) and (B).

Description

The present invention relates to a powder sludge coating composition and in particular a powder sludge coating composition which is dispersible the resin in water is excellent and after baking it with a hardened film can provide excellent strength.

Powder sludge coatings to be applied are in the form of a dispersion of fine Resin particles in water. In such coatings, various additives, such as surfactants, thickeners and the like, used to prevent the fine resin particles from aggregating or falling out, and around them keep stable dispersed in water (see, for example, Japanese Patent Laid-Open No. 2001-220544 and Japanese Patent Laid-Open No. 7-196953 (1995), pp. 3-4.)

These powder sludge coatings should prevent the The basic component and the hardening agent react with each other during storage.

Therefore, the functional group of the curing agent is blocked for use (see for example, Japanese Patent Laid-Open No. 7-196953 (1995), pp. 3-4.)

However, if the powder slurry coatings with surfactants are in the Practice can use the surfactants after evaporation of the medium water remain dry, the water resistance of the film deteriorate. The surfactants can also have a plasticizing effect develop, which degrades the strength of the film.

In addition, the powder slurry coatings with the curing agent require one blocked functional group a higher baking temperature at the practical Use because the blocking agent generally has a very high temperature of 160 ° C or higher is required for it to respond fully after dissociation. Such a high one Baking temperature can increase productivity due to the longer time required for heating or Cooling down after hardening may decrease and also discoloration of the film after the Cause burn-in. The heat source that is required for such a high temperature is also undesirable from an environmental point of view.

If the film created by applying and baking the slurry coating is outer When exposed to environmental influences, it needs resistance to acid rain. The Additives such as surfactants and thickeners that remain in the film, generated from the conventional sludge coatings, however clot when the acid rain evaporates, and therefore the appearance and the Deteriorate quality of the film.

It is an object of the present invention to solve the problems described above and a powder slurry coating that can provide a film that is excellent in terms of water resistance and strength Powder sludge coating that can be baked at a lower temperature, and a powder sludge coating, which has excellent resistance to acid rain can provide.

The inventors have and have carried out vigorous investigations to solve the problems the present invention accomplished. The present invention thus aims at one in water a dispersed powder slurry coating comprising: (A) a particulate material, which (a1) comprises a resin having an active hydrogen atom; (B) a reactive, surfactant with at least one ingredient from an optionally blocked isocyanate group and an epoxy group; and (M) an aqueous medium, in which contain the particulate material and the reactive surfactant are.

The present invention also aims at a film made by application and baking of the above water-dispersed powder slurry coating.

The present invention is described in detail below.

In the present invention, the reactive surfactant (B) comprises preferably a hydrophobic unit and a hydrophilic unit and preferably has at least one component from an optionally blocked isocyanate group and one Epoxy group in the hydrophobic unit. The hydrophobic unit preferably has an aromatic ring containing hydrocarbon residue of 6 to 100 Carbon atoms and at least one component from an optionally blocked Isocyanate group and an epoxy group. The hydrophilic unit is preferably a Component selected from an oxyethylene unit, an anionic radical, one cationic residue and an amphoteric ionic residue.

As for the present invention, the reactive surfactant will be described below Substance (B) with an oxyethylene unit in the hydrophilic unit as a reactive, surface active substance (B1); becomes the reactive, surface-active substance (B) with a component selected from an anionic radical, a cationic radical and an amphoteric ionic residue, in the hydrophilic unit as a reactive, surface active substance (B2); and becomes the reactive. surfactant (B1) with a component selected from an anionic radical, a cationic Residue and an amphoteric ionic residue, as a reactive, surface-active substance (B3) designated.

Regarding the water resistance of the film, which resulted from the aqueous dispersion The number of times the reactive surface-active substance (B) was produced the at least one component from an optionally blocked isocyanate group and one epoxy group per one molecule of the reactive surfactant (B) preferably 1 to 20, more preferably 1 to 15, particularly preferably 1 to 10, most strongly preferably 1 to 5.

The hydrophilic unit of the reactive surfactant (B) preferably comprises one or more hydrophilic residues of an oxyethylene unit, such as one polyoxyethylene; an anionic residue; a cationic residue; and one amphoteric ionic residues.

If the hydrophilic residue is the oxyethylene unit, the content is Oxyethylene unit, based on the weight of the reactive surfactant (B), preferably 20% by weight or more, more preferably 30% by weight or more, particularly preferably 50% by weight or more; preferably 90% by weight or less, more preferably 85% by weight or less, particularly preferably 80% by weight or less. On Oxyethylene content from 20 to 90% by weight can provide a slurry coating that has a great emulsifying ability and is stable.

In the present invention, the reactive surfactant (B) has one or more hydrophobic units. Examples of the hydrophobic unit include one aromatic ring-containing hydrocarbon radical having 6 to 100 or more, preferably 8 to 80 carbon atoms and with at least one constituent from one optionally blocked isocyanate group and an epoxy group in the molecular structure on. Examples of the aromatic ring-containing hydrocarbon group include styrylated phenyl radicals; residues of bisphenols free of hydroxyl groups, such as bisphenol A, Bisphenol S and bisphenol F; and vinyl monomer adducts thereof.

The hydrophobic unit can also be a hydrophobic oxyalkylene unit, such as one Oxypropylene unit and an oxytetramethylene unit.

Any method can be used without limitation to whichever is blocked To introduce the isocyanate group or the epoxy group or both into the hydrophobic unit, for example including the addition polymerization of at least one component from (b2) an optionally blocked isocyanate monomer which has a double bond and (b2 ') a vinyl monomer having an epoxy group with each other unsaturated monomer.

Examples of the isocyanate compound having the double bond include Isocyanatoethyl (meth) acrylate, isocyanatopropyl (meth) acrylate, isocyanatobutyl (meth) acrylate, Isocyanatohexyl (meth) acrylate, 3-isopropenyl-α, α-dimethylbenzyl isocyanate, 3-ethyleneylα, α-dimethylbenzyl isocyanate and any combination of two or more thereof.

Preferred examples include 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 3- Ethyleneyl-α, α-dimethylbenzyl isocyanate.

Examples of the blocking agent for the isocyanate group include lactams such as ε- Caprolactam, δ-valerolactam and γ-butyrolactam; Phenols, such as phenol, cresol, Ethylphenol, butylphenol, nonylphenol and dinonylphenol; Oximes like Methyl ethyl ketone oxime, acetophenone oxime and benzophenone oxime; Alcohols, such as methanol, Ethanol, butanol and cyclohexanol; Diketones, such as dimethyl malonate, diethyl malonate, Methyl acetoacetate, ethyl acetoacetate and acetylacetone; Mercaptans such as butyl mercaptan and dodecyl; Uretdiones such as isophorone diisocyanate dimer and Hexamethylendiisocyanatdimer; Amides such as acetanilide and acetamide; Imides how Succinimide and maleimide; Sulfites such as sodium bisulfite; and any combination of two or several of them.

Preferred examples include alcohols, lactams, oximes and phenols and methanol, Ethanol and methyl ethyl ketone oxime are particularly preferred.

The vinyl monomer (b2 ') having the epoxy group can be any known compound be the epoxy group and a polymerizable vinyl group in the molecular structure having. Examples of the vinyl monomer (b2 ') include glycidyl esters of unsaturated ones Carboxylic acids, such as glycidyl (meth) acrylate, glycidyl-α-ethyl acrylate, Glycidyl-α-n-propyl acrylate, glycidyl-α-n-butyl acrylate, (meth) acrylate-3,4-epoxybutyl, (meth) acrylate-4,5- epoxypentyl, (meth) acrylate-6,7-epoxyheptyl, α-ethyl acrylate-6,7-epoxyheptyl, Methylglycidyl (meth) acrylate; and unsaturated glycidyl ethers, such as styrene-p-glycidyl ether, 2,3-diglycidyloxystyrene, 4-vinyl-1-cyclohexene-1,2-epoxide, 3,4-diglycidyloxystyro1,2,4- Diglycidyloxystyrene, 3,5-diglycidyloxystyrene, 2,6-diglycidyloxystyrene, 2,3- Dihydroxymethylstyrene diglycidyl ether, 3,4-dihydroxymethylstyrene diglycidyl ether, 2,4- Dihydroxymethylstyrene diglycidyl ether, 3,5-dihydroxymethylstyrene diglycidyl ether, 2,6- Dihydroxymethylstyrene diglycidyl ether, 2,3,4-trihydroxymethylstyrene triglycidyl ether, 1,3,5 - Trihydroxymethylstyrene triglycidyl ether, 5-vinylpyrogallol triglycidyl ether, 4- Vinyl pyrogallol triglycidyl ether and vinyl fluoroglycinol triglycidyl ether.

Usable examples of the other unsaturated monomer include an aliphatic Vinyl hydrocarbon, an alicyclic vinyl hydrocarbon and an aromatic Vinyl hydrocarbon, but is not limited to this.

Examples of the aliphatic vinyl hydrocarbon include ethylene, propylene, butene, Isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene and other α-olefins. Examples of the alicyclic vinyl hydrocarbon include cyclohexene, (di) cyclopentadiene, pinene, Limonene, indene, vinylcyclohexene and ethylidene bicycloheptene. Examples of the aromatic vinyl hydrocarbon include styrene, α-methylstyrene, vinyl toluene, 2,4- Dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, Benzylstyrene, crotylbenzene, vinylnaphthalene, divinylbenzene, divinyltoluene, divinylxylene, Divinyl ketone and trivinyl benzene.

In the present invention, for example, the non-ionic, reactive, surfactant (B1) preferably (L) a urethane resin with at least one Part of an optionally blocked isocyanate group and an epoxy group. The urethane resin (L) comprises: (b3) a product of an addition reaction of (b1) one monohydric phenol or a monohydric aromatic alcohol and at least one Component from (b2) a vinyl monomer with an optionally blocked Isocyanate group and (b2 ') a vinyl monomer having an epoxy group, or a Alkylene oxide adduct of the product of the addition reaction; (b4) an organic diisocyanate; and (b5) at least one constituent of a diol and a diamine, each with one Polyoxyalkylene chain including a polyoxethylene unit as main components and optionally, (b10) a chain extension agent or (b 11) a agent for Use chain termination or both.

The weight average molecular weight of the non-ionic, reactive, surfactant (B1) is preferably 1,000 to 150,000, more preferably 5,000 to 100,000, particularly preferably 10,000 to 25,000. A weight average of the Molecular weight of 1,000 or more is preferred because it is sufficient Surface activity can be provided. A weight average molecular weight of 150,000 or less is preferred because the resulting aqueous resin dispersion has a have low viscosity and can be stable. The weight average of the Molecular weight can be measured using gel permeation chromatography (GPC). With this technique, the polymer solution will run on the column loaded with polystyrene gel left and the concentration and molecular weight of the polymer in the eluate are expressed as Function of the amount of elution determined.

In the addition reaction of the monohydric phenol or the monohydric aromatic Alcohol (b1) can contain at least one component of vinyl monomer (b2) and vinyl monomer (b2 ') in combination with (b9) a vinyl monomer without isocyanate group or Epoxy group, as required.

Any monohydric phenol or monohydric aromatic alcohol (b1) can be without Limit used to be the non-ionic, reactive, surfactant (B1), for example including phenol, alkyl (C1 to C18) phenol, such as Nonylphenol, dodecylphenol and octylphenol; arylalkylated phenol such as cumylphenol;

Alkyl (C1 to C18) ethers of bisphenols, such as monomethyl ether of bisphenol A, Monobutyl ether of bisphenol A and monobutyl ether of bisphenol S; and each Combination of two or more of them.

Preferred examples include phenol and cumylphenol.

Examples of the monohydric aromatic alcohol include benzyl alcohol, 2- Biphenylethanol and 4-biphenylethanol.

Preferred examples include benzyl alcohol.

Examples of the vinyl monomer (b2) include the above isocyanate compounds, which have the double bond.

Preferred examples of such a vinyl monomer include 3-isopropenyl-α, αdimethylbenzyl isocyanate and 3-ethyleneyl-α, α-dimethylbenzyl isocyanate.

The vinyl monomer (b2 ') can be any known compound having an epoxy group and has a polymerizable vinyl group in the molecular structure, for example including the above vinyl monomers having the epoxy group.

Preferred examples of the vinyl monomer (b2 ') include styrene p-glycidyl ether and 2,3- Diglycidyloxystyrene.

Examples of the optionally used vinyl monomer without isocyanate group or Epoxy group (b9) include but are not the above unsaturated monomers limited to this.

Preferred examples of the monomer (b9) include styrene.

The product of the addition reaction or its alkylene oxide adduct (b3) can be used with any Method of adding a monohydric phenol or a monohydric aromatic Alcohol (b1) to the vinyl monomer (b2) or vinyl monomer (b2 ') and optionally that Vinyl monomer (b9) are generated. Such a method preferably includes one Friedel-Crafts reaction, but is not limited to this.

Any known Friedel-Crafts reaction method can be used, for example including the polyaddition of the monohydric phenol or the monohydric aromatic Alcohol (b1) to at least one component from the vinyl monomer (b2), which the optionally blocked isocyanate group, and the vinyl monomer (b2 '), which Epoxy group, and optionally the vinyl monomer (b9) using any known Lewis acid catalyst such as iron chloride and aluminum chloride.

In the present invention, the product of the addition reaction by Add the monohydric phenol or the monohydric aromatic alcohol (b1) at least one component of the vinyl monomer (b2) and the vinyl monomer (b2 ') and optionally the vinyl monomer (b9) was produced, an alkylene oxide was further added are produced, whereby the alkylene oxide adduct (b3) is generated.

Any alkylene oxide (hereinafter abbreviated as "AO", having 1 to 30 carbon atoms) can can be used without limitation, for example including ethylene oxide (hereinafter abbreviated as "EO"), propylene oxide (hereinafter abbreviated as "PO"), 1,2-, 1,3- or 2,3- Butylene oxide, tetrahydrofuran, α-olefin (C4 to C30) oxide, epichlorohydrin, styrene oxide and any combination of two or more of them. Preferred examples include EO. The type of addition is preferably statistical addition or block addition or both.

The alkylene oxide added may be 1 to 30 mol, preferably 1 to 10 mol, more preferably 1 to 5 mol.

This is in the product of the addition reaction or the alkylene oxide adduct thereof (b3) Weight ratio of the basic units: monovalent phenol or monovalent aromatic Alcohol (b1) / at least one component of vinyl monomer (b2) and vinyl monomer (b2 ') / optional vinyl monomer (b9) / added AO preferably (1 to 5) / (1 to 20) / (0 to 20) / (0 to 50), more preferably (1 to 3) / (1 to 10) / (1 to 10) / (1 to 25).

• 1. aliphatische Diisocyanate mit 2 bis 18 Kohlenstoffatomen (wobei das Kohlenstoffatom in der NCO-Gruppe nicht gezählt wird (nachstehend in der gleichen Weise)), wie Ethylendiisocyanat, Tetramethylendiisocyanat, Hexamethylendiisocyanat (HDI), Dodecamethylendiisocyanat, 2,2,4-Trimethylhexamethylendiisocyanat, Lysindiisocyanat, 2,6-Diisocyanatomethylcaproat, Bis(2-isocyanatoethyl)fumarat, Bis(2- isocyanatoethyl)carbonat und 2-Isocyanatoethyl-2,6-diisocyanatohexanoat;
• 2. alicyclische Diisocyanate mit 4 bis 15 Kohlenstoffatomen, wie Isophorondiisocyanat (IPDI), Dicyclohexylmethan-4,4'-diisocyanat (hydriertes MDI), Cyclohexylendiisocyanat, Methylcyclohexylendiisocyanat (hydriertes TDI) und Bis(2-isocyanatoethyl)-4-cyclohexen;
• 3. aromatische Diisocyanate mit 6 bis 14 Kohlenstoffatomen, wie 1,3- oder 1,4- Phenylendiisocyanat, 2,4- oder 2,6-Tolylendiisocyanat (TDI), rohes TDI, 2,4'- oder 4,4'- Diphenylmethandiisocyanat (MDI), 4,4'-Diisocyanatobiphenyl, 3,3'-Dimethyl-4,4' - diisocyanatobiphenyl, 3,3'-Dimethyl-4,4'-diisocyanatodiphenylmethan, rohes MDI und 1,5- Naphthylendiisocyanat;
• 4. aromatisch-aliphatische Diisocyanate mit 8 bis 15 Kohlenstoffatomen, wie m- oder p- Xylylendiisocyanat (XDI) und α,α,α',α'-Tetramethylxylylendiisocyanat (TMXDI);
• 5. Modifikationen dieser Diisocyanate, wie solche mit einer Carbodiimidgruppe, einer Uretdiongruppe, einer Uretimingruppe oder einer Harnstoffgruppe; und
• 6. jede Kombination von zwei oder mehreren aus ((1) bis (5)).

Examples of the organic diisocyanate (b4) include, but are not limited to:

• 1. aliphatic diisocyanates having 2 to 18 carbon atoms (the carbon atom in the NCO group not being counted (in the same manner below)), such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate;
• 2. alicyclic diisocyanates with 4 to 15 carbon atoms, such as isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI) and bis (2-isocyanatoethyl) -4-cyclohexene;
• 3. aromatic diisocyanates with 6 to 14 carbon atoms, such as 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- or 4,4'- Diphenylmethane diisocyanate (MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, crude MDI and 1,5-naphthylene diisocyanate;
• 4. aromatic-aliphatic diisocyanates with 8 to 15 carbon atoms, such as m- or p-xylylene diisocyanate (XDI) and α, α, α ', α'-tetramethylxylylene diisocyanate (TMXDI);
• 5. Modifications of these diisocyanates, such as those with a carbodiimide group, a uretdione group, a uretimine group or a urea group; and
• 6. any combination of two or more of ((1) to (5)).

Preferred examples include HDI, TDI and IPDI.

With regard to the emulsifiability of the above component (B), the content is the polyoxyethylene unit in at least one component of a diol and one Diamine (b5) with the polyoxyalkylene chain preferably 20 to 100% by weight, more preferably 50 to 100 wt .-%, particularly preferably 70 to 100 wt .-%, based on the weight of at least one component from a diol and a diamine (b5).

Examples of the diol and diamine (b5) include (b5-1) having hydroxyl groups terminated polyether diol, (b5-2) a hydroxyl terminated polyester diol and (b5-3) a polyether diamine terminated with amino groups. It can do the diol alone Diamine alone or both the diol and the diamine can be used.

As the polyether diol (b5-1), for example, a low molecular weight diol, a compound having the structure of a dihydric phenol with AO added, or Combination of these can be used.

Examples of the low molecular weight diol include ethylene glycol (hereinafter abbreviated as "EG"); diethylene glycol; Propylene glycol; dipropylene; 1,4- Butanediol (hereinafter abbreviated as "14BG"); 1,3-butanediol; neopentyl glycol; 1,6- hexanediol; Low molecular weight diols with a cyclic radical, such as those in US Pat Japanese Patent Publication No. 45-1474 (1970);

Bis (hydroxymethyl) cyclohexane; Bis (hydroxyethyl) benzene; and ethylene oxide adducts of Bisphenol A; and any combination of two or more of them, but are not on it limited.

Usable examples of the dihydric phenol to which the AO is to be added include, but are not limited to, a dihydric phenol of 6 to 30 carbon atoms limited. Examples of the dihydric phenol include monocyclic dihydric Phenols such as pyrocatechol, resorcinol and hydroquinone; divalent condensed Ring compounds such as dihydroxynaphthalene; Bisphenols, such as bisphenol A. bisphenol F, Bisphenol 8. dihydroxydiphenyl ether and dihydroxydiphenyl thioether; binaphthol; and with Alkyl (C1 to C10) or halogen (such as chlorine and bromine) substituted compounds thereof, such as brominated bisphenol A.

Examples of the polyester diol (b5-2) include condensed polyester diols the reaction of the polyether diol (b5-1), which is a number average molecular weight of 1,000 or less, with a dicarboxylic acid or a low diol Molecular weight or both are generated and which the polyoxyethylene unit in the have the manner described above.

Examples of the low molecular weight diol include those above described one.

Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, Adipic acid, azelaic acid and sebacic acid; aromatic dicarboxylic acids, such as Terephthalic acid, isophthalic acid and phthalic acid; Derivatives of these dicarboxylic acids, from which can produce esters such as acid anhydrides and lower alkyl (C1 to C4) esters; and each Combination of two or more of them.

As the polyether diamine (b5-3), the product can be used by modification of the polyether diol (b5-1) is obtained, the terminal hydroxyl group becoming a Amino group is modified.

Any known method can be used to isolate the terminal hydroxyl group Modify amino group. In a special procedure, the terminal Hydroxyl group of the polyether diol (b5-1) is converted into a terminal cyanoalkyl group which is reduced to an aminoalkyl group. In a more specific process, that is Polyether diol (b5-1) with the terminal hydroxyl group with acrylonitrile or nonennitrile implemented and the cyanoethyl compound generated is hydrogenated.

A preferred method includes the steps of transferring the terminal hydroxyl group into a cyanoalkyl group in polyether diol (b5-1) and reducing the terminal Cyanoalkyl group to an aminoalkyl group.

The number average molecular weight of the diol and diamine (b5) is one Hydroxyl or an amino group preferably 100 to 10,000 or more, more preferably 400 to 4,000.

Close examples of chain extension agent (b10) that may be used Water; the above low molecular weight diols; Diamines such as aliphatic Diamines of 2 to 6 carbon atoms, such as ethylenediamine and 1,2-propylenediamine; alicyclic diamines with 6 to 15 carbon atoms, such as isophoronediamine and 4,4'- diaminodicyclohexylmethane; and aromatic diamines having 6 to 15 carbon atoms, such as 4,4'-diaminodiphenylmethane; Monoalkanolamines such as monoethanolamine; Hydrazine or its derivatives, such as dihydrazidadipate; and any combination of two or more of them on. The low molecular weight diols are preferred and EG and 14BG are particularly preferred.

Examples of the means for chain termination (b11) include (b11-1) a monovalent one aliphatic alcohol and (b11-2) an aliphatic monoamine limited.

Examples of the monohydric aliphatic alcohol (b11-1) include saturated aliphatic monohydric alcohols with 1 to 18 carbon atoms, such as ethyl alcohol, propyl alcohol, Butyl alcohol, octyl alcohol, lauryl alcohol, 2-octyl alcohol and 2-ethylhexyl alcohol; and unsaturated aliphatic monohydric alcohols with 1 to 18 carbon atoms, such as Oleyl alcohol.

Examples of the aliphatic monoamine (bll-2) include aliphatic monoamines with 1 up to 18 carbon atoms, such as octylamine, 2-ethylhexylamine, dodecylamine, dibutylamine, Dioctylamine and di (2-ethylhexyl) amine; unsaturated aliphatic monoamines with 1 to 18 Carbon atoms such as oleylamine; and monoamines containing hydroxyalkyl groups 1 to 16 carbon atoms such as monoethanolamine and diethanolamine.

The monohydric aliphatic alcohols and the aliphatic monoamines are preferred and the monohydric aliphatic alcohols are particularly preferred.

In the present invention, the urethane resin (L) is preferably the compound of the general formula (1):


where Q is a residue (b3) of a product of an addition reaction of (b1) a monohydric phenol or a monohydric aromatic alcohol and at least one component from (b2) a vinyl monomer with an optionally blocked isocyanate group and (b2 ') a vinyl monomer with an epoxy group, or an alkylene oxide adduct of the product of the addition reaction, G is a radical (b4) of an organic diisocyanate which may have a urea bond, X is O or NH, J is a radical (b5) of at least one component from a diol and a diamine which each have a polyoxyalkylene chain which includes a polyoxyethylene unit, Z represents a hydrogen atom or a radical represented by -COO-Q or -CO-Y, where Y is a radical -OR ¹ , where R 'is a monohydric alcohol radical with 1 to 18 carbon atoms or a radical -NR ² R ³ , where R ^{2 is} a hydrocarbon radical having 1 to 18 carbon atoms or a Is hydroxyalkyl of 1 to 16 carbon atoms, and R ^{3 is} hydrogen, a hydrocarbon of 1 to 18 carbon atoms or a hydroxyalkyl of 1 to 16 carbon atoms, and m is an integer of 1 to 500.

In the present invention, the urethane resin (L) can be used without any method Limitation. According to a conventional method for the synthesis of Polyurethane resins (like a one-step process or a multi-step process) will Product of an addition reaction or its alkylene oxide adduct (b3) with the organic Diisocyanate (b4) and at least one component from the diol and the amine (b5) and if necessary, the agent for chain extension (b10) and the agent for chain termination (b11) reacted, whereby the urethane resin (L) is formed. The reaction temperature for Formation of the urethane is preferably 30 to 200 ° C, more preferably 50 to 180 ° C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 to 8 Hours.

The urethane formation reaction is preferably carried out in a solvent-free system or in performed an organic solvent that is not reactive to the isocyanate is. Examples of such an organic solvent include acetone, tetrahydrofuran, Dimethylformamide, dimethyl sulfoxide, toluene and dioxane. After generating the Urethane resin (L), the organic solvent is preferably by evaporation away.

In the urethane formation reaction, the equivalent ratio of the hydroxyl group (OH) and the amino group (NH ₂ ) to the isocyanate group (NCO) of the organic diisocyanate (b4) [(OH + NH ₂ ): NCO] is preferably 1: (0.8 to 1.5 ), more preferably 1: (0.9 to 1.3). When the equivalent ratio of the NCO group is 0.8 to 1.5, the resulting polyurethane resin can have a balanced molecular weight, and the resulting aqueous resin dispersion can provide a film with good water resistance.

In the present invention, the reactive surfactant (B2) having an anionic, cationic or amphoteric ionic unit can include any hydrophilic residue without limitation. Examples of such a hydrophilic group include anionic groups such as a carboxylate group (-COO ^- X ⁺ ), a sulfonate group (-SO ₃ ^- X ⁺ ), a sulfate ester salt group (-OSO ₃ ^- X ⁺ ), a phosphate ester salt group (-OPO ₃ H ^- X ⁺ or -OPO ₃ ^2- .2X ⁺ ), where X can be sodium, potassium, ammonium, alkanolamine salt or the like; cationic groups such as a primary amine salt group, a secondary amine salt group, a tertiary amine salt group and a quaternary amine salt group; and amphoteric ionic residues such as betaine residue, but are not limited to this.

The content of the hydrophilic residue, based on the weight of the reactive, surfactant (B2) is preferably 0.1% by weight or more, more preferably 1% by weight or more, particularly preferably 5% by weight or more; preferably 50 % By weight or less, more preferably 20% by weight or less, particularly preferably 10 % By weight or less. If the content of the hydrophilic residue is 0.1 to 50% by weight , the resulting slurry coating can have a large emulsifying ability and be stable.

The reactive, surface-active substance (B2) preferably has a weight average of Molecular weight of 300 to 100,000, more preferably 800 to 50,000, especially preferably 1,000 to 8,000. A weight average molecular weight of 300 or more is preferred because sufficient surface activity can be obtained. On Weight average molecular weight of 100,000 or less is preferred because the resulting aqueous resin dispersion have a low viscosity and be stable can.

For example, in the present invention, the reactive surfactant includes (B2) as main components preferably: (b3 ') a residue of a product one Addition reaction of the (b1) monohydric phenol or the monohydric aromatic alcohol and at least one component from (b2) a vinyl monomer with an optionally blocked isocyanate group and (b2 ') a vinyl monomer with an epoxy group, or a residue of an alkylene oxide adduct of the product of the addition reaction; and at least an ionic radical which is selected from an anionic radical, a cationic residue and an amphoteric ionic residue.

At least one ionic radical selected from the anionic radical, the cationic radical and the amphoteric ionic residue can be added at any point in the residue (b3 '). For example, such an ionic radical on the aromatic ring, the Hydroxyl group, which differs from monovalent phenol or monovalent aromatic Alcohol (b1) is derived, or the hydroxyl group, by the addition of the alkylene oxide the above hydroxyl group is formed, are added.

In the present invention, any method can be used without limitation, to make the reactive surfactant (B2). For example, that Product of the addition reaction or the alkylene oxide adduct thereof (b3) at its terminal Hydroxyl group made anionic (B2-1), cationic (B2-2) or amphoteric ionic (B2-3) to form the reactive surfactant (B2).

In an example of the process for the preparation of the anionically made, reactive, surfactant (B2-1) becomes the terminal hydroxyl group of the product of Addition reaction or the alkylene oxide adduct thereof (b3) with sulfuric anhydride, Chlorosulfonic acid or the like converted to a sulfate ester or with Phosphoric anhydride or the like converted to a phosphate ester. The The reaction temperature is preferably 20 ° C to 200 ° C, more preferably 20 ° C to 100 ° C. The reaction time is preferably 0.1 to 30 hours, more preferably 0.1 up to 10 hours.

In one example of the process for making the cationic reactive surfactant (B2-2), the aminated terminal end of the addition reaction product or alkylene oxide adduct thereof (b3) is neutralized with acid or quaternized with an alkylating agent. Any acid can be used for neutralization without limitation, for example including hydrochloric acid and acetic acid. Examples of the alkylating agent for quaternization include methyl chloride, methyl bromide, benzyl chloride, long chain alkyl chloride, epichlorohydrin, dimethyl sulfate and ethylene oxide. In an example of the method for amination of the terminal end, acrylonitrile is added dropwise to the product of the addition reaction or the alkylene oxide adduct thereof (b3) in the presence of an alkaline catalyst such as potassium hydroxide at a temperature of 10 to 80 ° C so that the acrylonitrile to the Hydroxyl group of the reactant is added, and then after removing the alkali catalyst, the product to which acrylonitrile has been added is in a solvent such as methanol with a catalyst such as nickel or cobalt under high pressure such as a pressure of 30 to 100 kg / cm ² , hydrogenated.

The reaction temperature for neutralization is preferably 20 to 150 ° C, higher preferably 20 to 100 ° C, and the reaction time is preferably 0.1 to 20 hours, more preferably 0.1 to 6 hours.

The reaction temperature with the alkylating agent is preferably 50 to 300 ° C. more preferably 80 to 150 ° C, and the reaction time is preferably 0.1 to 20 Hours, more preferably 0.1 to 12 hours.

Examples of the process for the preparation of the amphoteric ionically reacted surfactant (B2-3) include a process in which the terminal Amino group of the addition reaction product or alkylene oxide adduct thereof (b3) is made tertiary with the alkylating agent and then with an aqueous solution of Sodium monochloroacetate is implemented; and a method based on the Addition reaction of an ester containing vinyl groups or a vinyl group containing nitrile is followed by saponification with alkali. Examples of the vinyl groups containing esters include methyl acrylate and acrylonitrile.

In the present invention, the OH-terminated, non-ionic reactive, surface-active substance (B1) implemented and in the reactive, surface-active substance (B3) with at least one component selected from anionic radical, cationic radical and amphoteric ionic residue. This procedure can be done according to the procedure for the reactive, surface-active substance (B2).

In the present invention, the content of the anionic residue is cationic residue or amphoteric ionic radical in the reactive surfactant (B3) is preferred 0.1% by weight or more, more preferably 1% by weight or more, particularly preferably 5% by weight or more; preferably 50% by weight or less, more preferably 20% by weight or less, particularly preferably 10% by weight or less, based on the weight of the reactive, surface-active substance (B3). If the hydrophilic residue content is 0.1% by weight is up to 50% by weight, the resulting slurry coating can be large Have emulsification ability and be stable.

The reactive, surface-active substance (B3) preferably has a weight average of Molecular weight of 1,000 to 100,000, more preferably 2,000 to 50,000, especially preferably 4,000 to 20,000 to a weight average molecular weight of 1,000 or more is preferred because sufficient surface activity can be obtained. On Weight average molecular weight of 100,000 or less is preferred because the resulting aqueous resin dispersion have a low viscosity and be stable can.

In the present invention, when the curing agent (a2) is blocked Has isocyanate group, a non-reactive, surface-active substance (B ') in combination be used. The reactive, surface-active substance (B) can in part by the non-reactive, surface-active substance (B ') can be replaced. When combining the reactive, surface-active substance (B) with the non-reactive, surface-active substance (B ') is the quantitative ratio (B' / B) of non-reactive, surface-active substance (B ') to the reactive surfactant (B), preferably not less than 0/1 and 0.8 / 1 or less, more preferably not less than 0.1 / 1 and 0.6 / 1 or less in terms of the water resistance.

Examples of the non-reactive surfactant (B ') include known ones surfactants such as non-ionic surfactants (B '(1)), anionic, surface-active substances (B '(2)), cationic, surface-active substances (B' (3)) and amphoteric, surface-active substances (B '(4)).

Examples of the nonionic surfactant (B '(1)) include nonionic, surfactants (B '(1) 1) of the type with added alkylene oxide and non-ionic, surfactants (B '(1) 2) of the polyhydric alcohol type.

Examples of the anionic surfactant (B '(2)) include carboxylic acids or Salts thereof (B '(2) 1), sulfate ester salts (B' (2) 2), salts of carboxymethyl compounds (B '(2) 3), sulfonate salts (B' (2) 4) and phosphate ester salts (B '(2) 5).

Examples of the cationic surfactant (B '(3)) include quaternary Ammonium salt types and amine salt types.

Examples of the amphoteric surfactant (B '(4)) for use in the The present invention includes (1) amphoteric surfactants from Carboxylate salt type, (2) amphoteric, sulfate ester salt type surfactants, (3) sulfonate salt type amphoteric surfactants and (4) amphoteric, phosphate ester salt type surfactants.

In the present invention, the HLB value of the reactive surfactant (B) or the non-reactive surfactant (B ') is preferably 5 to 40, more preferably 5 to 20, in view of the emulsifiability for the ethylenically unsaturated monomer and the process for Disperse the resin particles to form a stable, aqueous dispersion or emulsion. The HLB value can be adjusted by modulating the type and content of the hydrophobic residue or hydrophilic residue. For example, the HLB value can be determined according to Oda's method, the fully revised version in Takehiko Fujimoto, "Shin Kaimenkasseizai Nyumon" (in Japanese) (new introduction to surfactants), Sanyo Chemical Industries, Ltd., 1992, p. 197 , is described. In this method, an organic (hydrophobic) value and an inorganic (hydrophilic) value are obtained from the type and content of the hydrophobic and hydrophilic residues in the above component (B) using the organic reference value and the inorganic reference value, each for each functional group can be estimated from the number of carbon atoms (for example, these values are listed in Table 3.3.11 of the previous text), and the HLB value is calculated from these values using the following formula:

HLB = 10 × (inorganic value / organic value)

In the sludge coating according to the invention, the particulate material (A) comprises the resin (a1) containing an active hydrogen atom and preferably contains that Hardening agent (a2). For example, the resin (a1) and the curing agent (a2) preferably mixed together by being dissolved in an organic solvent be melted or kneaded.

For example, the particulate material (A) can be processed using a method in which solution the resin (a1) in a solvent and preferably the curing agent (a2) in water dispersed and the solvent removed, or obtained by a method in which the resin (a1) and preferably the curing agent (a2) is melted and kneaded and the resulting product is pulverized. In another embodiment can, as described below, the particulate material (A) in the process for Production of the slurry coating can be generated, which involves the steps of dispersing a Solution of the resin (a1) in a solvent and preferably the curing agent (a2) in an aqueous (M) containing the reactive surfactant (B) and Includes removal of the solvent.

In the sludge coating according to the invention, the particulate material (A) can be of indefinite shape, but is in terms of smoothness and uniformity of the film preferably spherical in shape. The term "spherical shape" here refers to the Particle shape with a major axis / minor axis ratio in the range of 1.0 to 1.5.

In the sludge coating according to the invention, the particulate material (A) preferably an average particle diameter of 0.1 to 50 µm, more preferably 0.5 up to 20 µm. even more preferably 1.0 to 10 µm. The particle diameter can be Measurement with an electron microscope, sedimentation process, electrozone process, dynamic light scattering methods or the like can be determined and the dynamic Light scattering is preferred because it has a suitable range for measuring the Can provide particle size.

The particulate material (A) can have a spherical shape with a Have major axes / minor axes ratio of 1.0 to 1.5, preferably 10 to 1.2. The Major axes / minor axes ratio can be seen with the steps of viewing the particle a light microscope as defined by Heywood, determine the minimum Distance between two parallel lines that tangent to the contour of the particle in the plane view, as a minor axis, determine the maximum distance between two parallel lines perpendicular to the above lines as the main axis and Calculate the ratio of the main axis thus determined to the secondary axis thus determined be preserved.

Examples of the solvent in which the resin containing an active hydrogen atom (a1) to be solved include aromatic hydrocarbon solvents, aliphatic or alicyclic hydrocarbon solvents, halide solvents, Ester solvent, ester ether solvent, ether solvent, ketone solvent, Alcohol solvents, amide solvents, sulfoxide solvents, heterocyclic Solvents from compounds and solvent mixtures of two or more of it. Preferred examples include ether solvents, ester ether solvents or aromatic hydrocarbon solvents.

Examples of the aromatic hydrocarbon solvents include toluene, xylene, Ethylbenzene and tetralin.

Examples of the aliphatic or alicyclic hydrocarbon solvents include n-hexane, n-heptane, mineral spirits and cyclohexane.

Examples of the halide solvents include methyl chloride, methyl bromide, Methyl iodide, methylene dichloride, carbon tetrachloride, trichlorethylene and perchlorethylene on.

Examples of the ester solvents include ethyl acetate and butyl acetate.

Examples of the ester ether solvents include methoxybutyl acetate, Methyl cellosolve acetate and ethyl cellosolve acetate.

Examples of the ether solvents include diethyl ether, tetrahydrofuran, dioxane, Ethyl cellosolve, butyl cellosolve and propylene glycol monomethyl ether.

Examples of the ketone solvents include acetone, methyl ethyl ketone, Methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone.

Examples of the alcohol solvents include methanol, ethanol, n-propanol, Isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol and benzyl alcohol on.

Examples of the amide solvents include dimethylformamide and dimethylacetamide on.

Examples of the sulfoxide solvents include dimethyl sulfoxide.

Examples of the heterocyclic compound solvents include N- Methylpyrolidone.

In the present invention, examples of the resin (a1) include the active one Hydrogen atom, such as that of an alcoholic hydroxyl group, a phenolic Hydroxyl group, an amino group, a carboxylic acid group, a phosphoric acid group, a thiol group or the like, (a1 (1)) an acrylic resin, (a1 (2)) a polyester resin, (a1 (3)) a polyurethane resin and (a1 (4)) an epoxy resin, provided that these resins are the have active hydrogen atom.

If the reactive surface-active substance (B) blocked if necessary Has isocyanate group, each of the above resins with the active Hydrogen atom preferably together with the reactive surface-active substance (B) is used and the acrylic resin (a1 (1)) is particularly preferred.

If the reactive surfactant (B) has the epoxy group, the resin is with the active hydrogen atom of the alcoholic hydroxyl group, the carboxylic acid group, the amino group or the thiol group, preferably together with the reactive, surfactant (B) and the acrylic resin (a1 (1)) with the active Hydrogen atom of the alcoholic hydroxyl group or the carboxylic acid group particularly preferred.

The equivalent of the active hydrogen atom in the resin (a1) is preferably 50 to 50,000, more preferably 100 to 10,000, still more preferably 200 to 5,000.

Examples of the monomer for producing the acrylic resin (a1 (1)) include (i) (a1 (1) 1) (Meth) acrylic acid or (meth) acrylate ester with a hydroxyl group, (ii) (a1 (1) 2) (Meth) acrylate esters without hydroxyl group, acrylamide or acrylonitrile and (iii) (a1 (1) 3) each other optional monomer.

The weight percent ratio of monomer (a1 (1) 1) / monomer (a1 (1) 2) / monomer (a1 (1) 3) in the acrylic resin (a1 (1)) is preferably (1 to 100) / (0 to 80) / (0 to 50), more preferably (1 to 50) / (1 to 50) / (0 to 20).

The acrylic resin (a1 (1)) is synthesized by any known polymerization method, such as Solution polymerization, bulk polymerization, suspension polymerization or the like, and the weight average of its molecular weight is preferably 1,000 to 200,000, more preferably 2,000 to 100,000, still more preferably 3,000 to 50,000.

Examples of the monomer (a1 (1) 1) include acrylic acid; methacrylic acid; and Hydroxyalkyl (C2 to C4) (meth) acrylate, such as 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.

Preferred examples include 2-hydroxyethyl (meth) acrylate.

Examples of the monomer (a1 (1) 2) include acrylamide; acrylonitrile; and (Meth) acrylate (cyclo) alkyl esters, such as esters of (meth) acrylic acid and alcohols with 1 to 25 Carbon atoms, such as methyl alcohol, ethyl alcohol, butyl alcohol, stearyl alcohol, Ethylene glycol, 1,4-butanediol, cyclohexanol and isoborneol.

Preferred examples include methyl (meth) acrylate and n-butyl (meth) acrylate.

Examples of the monomer (a1 (1) 3) include styrene, which is preferred.

Examples of the polyester resin (a1 (2)) include a condensed polyester produced by the reaction of a low molecular weight polyol or one Polyalkylenetherdiols or both ingredients, which is a weight average of Have a molecular weight of 5,000 or less with a polycarboxylic acid; one Polylactone diol generated by lactone ring opening polymerization; and one Polycarbonate diol produced by the reaction of a low molecular weight diol with a carbonate diester of a lower alcohol such as methanol.

Examples of the low molecular weight polyol include the low diols Molecular weight belonging to the above polyether diol (b5-1).

Examples of the polyalkylene ether diol having a weight average molecular weight of 5,000 or less include polytetramethylene ether glycol, polypropylene glycol, Polyethylene glycol and any combination of two or more thereof.

Examples of the polycarboxylic acid include aliphatic dicarboxylic acids such as Succinic acid, adipic acid, azelaic acid and sebacic acid; aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid and phthalic acid; Derivatives of these dicarboxylic acids which can produce esters, such as acid anhydrides and lower alkyl (C 1 to C 4) esters; and any combination of two or more of them. Examples of the lactone include ε- Caprolactone, γ-butyrolactone and δ-valerolactone and any combination of two or several of them.

The polyester can be made by any conventional method, such as one Process in which the low molecular weight polyol or the polyether polyol or both components with a weight average molecular weight of 5,000 or less with the polycarboxylic acid or its derivative, from which esters can be produced (such as an acid anhydride such as maleic anhydride or phthalic anhydride; a lower ester, such as dimethyl adipate or dimethyl terephthalate; or halide), or their acid anhydride and an alkylene oxide such as ethylene oxide or propylene oxide, or both is implemented (condensed) and the active hydrogen atom can remain by a Excess of a component, the polyol, or a process in which the lactone is added to the indicator (the low molecular weight diol or the Polyether diol or both, with a weight average molecular weight of 5,000 or less).

Examples of the polyester resin (a1 (2)) include polyethylene adipate diol, Polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, Polyethylene propylene adipate diol, polyethylene butylene adipate diol, Polybutylene hexamethylene adipate diol, polydiethylene adipate diol, Poly (polytetramethylene ether) adipate diol, polyethylene azelate diol, polyethylene sebacate diol, Polybutylene azelate diol, polybutylene sebacate diol, polycaprolactone diol or triol and Polyhexamethylene carbonate diol.

The component ratio of polyol to polycarboxylic acid in the hydroxyl groups containing polyester can with the molar ratio [OH] / [COOH] of the hydroxyl group [OH] to the carboxylic acid group [COOH], which is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, still more preferably 1.3 / 1 to 1.02 / 1. The The ratio of the other components can be in the same range, even if this Components differ from the above. The weight average of the Molecular weight of the polyester is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, more preferably 3,000 to 15,000.

Examples of the active hydrogen atom in the polyester resin (a1 (2)) include the terminal ones End groups of the alcohol-carboxylic acid polycondensation, such as the alcoholic Hydroxyl group and the carboxylic acid group.

Examples of the polyurethane resin (a1 (3)) include polyol and polyadducts Diisocyanate.

Examples of the diisocyanate include those described above. Examples of that Polyol includes the compounds having the structure in which an alkylene oxide (hereinafter abbreviated as AO) to a polyfunctional compound that is an active one Contains hydrogen atom is added, and any combination of two or more of them.

Examples of the polyfunctional compound containing an active hydrogen atom include (a1 (3) 1) polyhydric alcohols, (a1 (3) 2) polyhydric phenols, (a1 (3) 3) amines, (a1 (3) 4) polycarboxylic acids, (a1 (3) 5) phosphoric acids and (a1 (3) 6) polythiols.

Examples of the polyhydric alcohols (a1 (3) 1) include dihydric alcohols such as Ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, Diethylene glycol, neopentyl glycol, bis (hydroxymethyl) cyclohexane and Bis (hydroxyethyl) benzene; three- to eight-valent polyhydric alcohols, such as glycerol, Trimethylolpropane, pentaerythritol, diglycerol, α-methylglucoside, sorbitol, xylitol, mannitol, Dipentaerythritol, glucose, fructose and sucrose.

Examples of the polyhydric phenols (a1 (3) 2) include polyhydric phenols such as Pyrogallol, pyrocatechol and hydroquinone; and bisphenols such as bisphenol A, bisphenol F and bisphenol S, a.

Examples of the amines (a1 (3) 3) include ammonia; Alkylamines with 1 to 20 Carbon atoms such as butylamine; Monoamines such as aniline; aliphatic polyamines, such as Ethylene diamine, trimethylene diamine, hexamethylene diamine and diethylene triamine; heterocyclic polyamines such as piperazine, N-aminoethylpiperazine and others heterocyclic polyamines disclosed in Japanese Patent Publication No. S55-21044 (1980); alicyclic polyamines such as dicyclohexylmethane diamine and isophoronediamine; aromatic polyamines, such as phenylenediamine, tolylenediamine, Diethyltolylenediamine, xylylenediamine, diphenylmethane diamine, diphenyl ether diamine and Polyphenylmethanpolyamin; and alkanolamines, such as monoethanolamine, diethanolamine, Triethanolamine and triisopropanolamine.

Examples of the polycarboxylic acids (a1 (3) 4) include aliphatic polycarboxylic acids such as Succinic acid and adipic acid; and aromatic polycarboxylic acids, such as phthalic acid, Terephthalic acid and trimellitic acid.

Examples of the phosphoric acids (a1 (3) 5) include phosphoric acid, phosphorous acid and Phosphonic acid. Examples of the polythiols (a1 (3) 6) include polythiol compounds a, by the reaction of glycidyl group-containing compounds with Hydrogen sulfide are generated.

Two or more of the above containing an active hydrogen atom Connections can be used in combination.

Examples of the AO that adds to the compound containing an active hydrogen atom include ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- or 1,3- Butylene oxide. Tetrahydrofuran (THF), styrene oxide, α-olefin oxide and epichlorohydrin.

A single AO can be used alone or two or more AOs can be used Combination can be used. In the latter case, the AO can by block addition, such as End type, equilibrium type, and active secondary type, statistical addition or one Combination of how statistical addition followed by end addition, where 0 up to 50% by weight, preferably 5 to 40% by weight, of the ethylene oxide chain statistically in the molecule are distributed and 0 to 30 wt .-%, preferably 5 to 25 wt .-% of the EO chain to the terminal end of the molecule is added.

Preferred examples of the AO include EO alone, PO alone, THF alone Combination of PO and EO and a combination of PO or EO or both Ingredients and THF, the combination being statistical, block or a combination of it can be.

The AO can be attached to an active hydrogen atom by any conventional method containing compound can be added in a single stage or multiple stages without or with a catalyst, such as an alkaline catalyst, an amine catalyst or an acid catalyst (especially in a later stage for AO addition) Normal or elevated pressure is carried out.

The degree of unsaturation of the polyol is preferably as low as possible and is preferred 0.1 meq / g or less, more preferably 0.05 meq / g or less, still more preferred 0.02 meq / g or less.

The ratio of polyol to isocyanate can with the molar ratio [OH] / [NCO] Hydroxyl group [OH] to the isocyanate group [NCO] can be reproduced, which is preferred Is 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, still more preferably 1.3 / 1 to 1.02 / 1. The ratio of the other components can be in the same range, even if these Components differ from the above. The weight average molecular weight is preferably 1,000 to 50,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000.

Examples of the active hydrogen atom in the polyurethane resin (a1 (3)) include an active one Hydrogen atom, which is different from the compound containing an active hydrogen atom derives and is not present in the urethane bond; and the hydrogen atom in the Urethane binding.

Examples of the epoxy resin (a1 (4)) include addition condensation products of (a1 (4) 1) a polyepoxide and (a1 (4) 2) a polycarboxylic acid. This addition polymerization creates a hydroxyl group that carries the active hydrogen atom.

Examples of the active hydrogen atom in the epoxy resin (a1 (4)) include an alcoholic one active hydrogen atom generated by epoxidation.

Examples of the polycarboxylic acid (a1 (4) 2) include those described above. The Polyepoxide (a1 (4) 1) can be aliphatic, alicyclic, heterocyclic or aromatic.

Examples of the aromatic polyepoxide (a1 (4) 1) include glycidyl ether of polyhydric phenols, such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, Bisphenol B diglycidyl ether, bisphenol AD diglycidyl ether, bisphenol S diglycidyl ether, halogenated bisphenol A diglycidyl, tetrachlorobisphenol A diglycidyl ether, Catechol diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, Pyrogallol triglycidyl ether, 1,5-dihydroxynaphthalenediglycidyl ether, Dihydroxybiphenyl diglycidyl ether, octachlor-4,4'-dihydroxybiphenyl diglycidyl ether, Glycidyl ether of phenol or cresol novolak resins, a diglycidyl ether product by the reaction of 2 mol bisphenol A with 3 mol epichlorohydrin, polyglycidyl ether, generated by the condensation reaction of phenol with glyoxal, glutaraldehyde or Formaldehyde and polyphenol polyglycidyl ether generated by the condensation reaction of resorcinol and acetone, a.

In the present invention, examples of the aromatic polyepoxide also include Diglycidyl urethane compound produced by the addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate with glycidol, a glycidyl group-containing Polyurethane (pre) polymer produced by the reaction of the above two reactants with a polyol, and diglycidyl ether of bisphenol A alkylene oxide (ethylene oxide or Propylene oxide) adducts.

Examples of the heterocyclic polyepoxide (a1 (4) 1) include tris (glycidyl) melamine.

Examples of the alicyclic polyepoxide (a1 (4) 1) include vinylcyclohexene dioxide, Limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, Ethylene glycol bisepoxydicyclopentyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'- epoxy-6'-methylcyclohexane carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and Bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine. The alicyclic compound also includes at the core hydrogenated compounds of the above aromatic Polyepoxide compounds.

Examples of the aliphatic polyepoxide (a1 (4) 1) include polyglycidyl ether of polyhydric aliphatic alcohols, polyglycidyl esters of polyhydric fatty acids and aliphatic glycidylamines.

Examples of the polyglycidyl ethers of the polyhydric aliphatic alcohols include Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Tetramethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether and Sorbitol polyglycidyl ether.

Examples of the polyglycidyl ester of the polyhydric fatty acid include diglycidyl adipate on.

Examples of the aliphatic glycidylamine include N, N, N ', N'- Tetraglycidylhexamethylene diamine.

In the present invention, the aliphatic compounds also include Glycidyl (meth) acrylate (co) polymers.

Preferred examples include the condensation product of bisphenol A diglycidyl ether and be adipic acid.

The addition condensation produces the residue containing the active hydrogen atom and the resin (a1) with the active hydrogen atom with an active Provide hydrogen atom equivalent from 50 to 50,000. That's why his is Weight average molecular weight preferably 1,000 to 200,000, more preferably 2,000 to 100,000, more preferably 3,000 to 50,000.

If the reactive surface-active substance (B) blocked if necessary Has isocyanate group, the curing agent (a2) can be any compound, the two or carries several functional groups per molecule, compared to the active one Hydrogen atom are reactive, for example including a one if appropriate blocked isocyanate group-containing compound, an epoxy group-containing compound Compound, a melamine resin, a compound containing a silyl ether residue and a compound containing (hemi) acetal residue, but is not limited thereto.

Preferred examples include an optionally blocked isocyanate group containing connection.

Examples of the compound containing an optionally blocked isocyanate group include the above organic diisocyanates and modifications thereof, such as Urethane groups, carbodiimide groups, allophanate groups, urea groups, Modifications containing biuret groups, isocyanurate groups or oxazolidone groups;

HDI isocyanurate; HDI biuret; IPDI isocyanurate; IPDI biuret; raw MDI [phosgene Compounds of crude diaminodiphenylmethane (such as a condensation product of Formaldehyde and an aromatic amine (aniline) or a mixture thereof and a Mixture of diaminodiphenylmethane and a small amount (e.g. 5 to 20 Mass%) tri- or higher functional polyamine)]; Polyallyl polyisocyanate (PAPI) and blocked isocyanate compounds thereof.

Preferred examples include HDI isocyanurate and IPDI isocyanurate.

Examples of the blocking agent include those described above and each Combination of two or more of them.

The ratio of the resin (a1) containing an active hydrogen atom to Hardening agent (a2) with the optionally blocked isocyanate group can with the Molar ratio of active hydrogen atom of the resin (a1) to the isocyanate group of the Hardening agent (a2) are reproduced, which is preferably 1/1 or more and 2/1 or less, more preferably 1.2 / 1 or more and 1.8 / 1 or less, even more preferred Is 1.3 / 1 or more and 1.6 / 1 or less.

Examples of the compound containing an epoxy group include aliphatic, alicyclic, heterocyclic or aromatic polyepoxide compounds such as that above polyepoxide compounds.

Preferred examples include the polyglycidyl ethers of the polyhydric aliphatic Alcohols and the glycidyl ethers of the polyhydric phenols.

The ratio of the resin (a1) containing an active hydrogen atom to Hardener (a2) with the epoxy group can with the molar ratio of active Hydrogen atom of the resin (a1) to the epoxy group of the curing agent (a2) reproduced which is preferably 1/1 or more and 2/1 or less, more preferably 1.2 / 1 or more and 1.8 / 1 or less, more preferably 1.3 / 1 or more and 1.6 / 1 or less is.

If the reactive surfactant (B) has the epoxy group, it can Hardening agent (a2) can be any compound that has two or more functional groups per Carries molecule that are reactive to the active hydrogen atom, including the compounds described above, but not limited thereto.

Preferred examples include the epoxy group-containing compounds and the an optionally blocked isocyanate group-containing compounds.

In the sludge coating according to the invention, the content of reactive surfactant (B) based on the total weight of the particulate Material (A) and the reactive surfactant (B), preferably 0.1 to 10 % By weight, more preferably 0.5 to 8% by weight, most preferably 1 to 5% by weight. If the non-reactive, surface-active substance (B ') is used in combination, lies the Total content of reactive, surface-active substance (B) and non-reactive, surfactant (B ') preferably in the above range.

The resin content in the slurry coating of the present invention is preferably 20 to 75% by weight, more preferably 20 to 60% by weight. The dispersion preferably has a viscosity at 25 ° C of 10 to 100,000 mPa.s, more preferably 50 to 5,000 mPa.s. The resin in the slurry coating can have a particle diameter of 0.1 to 50 µm exhibit.

A resin content of 20 to 75 wt .-% can have a good dispersed state of the Provide particulate material (A) in water. A viscosity of the dispersion of 10 to 100,000 mPa.s can make handling the coating easier. A medium one Particle diameter of the particulate material (A) from 0.1 to 50 microns can Prevent the particles from falling out in water and prevent water evaporation when stoving and facilitate viscosity control.

Unless the beneficial effects of the present invention are worsened, can, if necessary, the reactive surfactant (B) in combination with each other known emulsifiers or surfactants can be used (including a nonionic emulsifier or surfactant, one anionic emulsifier or surfactant, a cationic Emulsifier or surfactant or various reactive emulsifiers or surfactants). The combined or other emulsifier content surfactant, based on the total weight of emulsifier or surfactant, is preferably 44% by weight or less, more preferably 37 wt% or less.

In the present invention, examples of the aqueous medium (M) include for example water or a mixture of water and a water-miscible one Solvents such as an alcohol (such as methanol or isopropanol) or a Ketone solvents such as acetone. The mixing ratio of water miscible Solvent / water is preferably 0.1 / 99.9 to 10/90.

In the present invention, examples of the catalyst (C) (c1) include cyclic Amidine, (c2) a cyclic tertiary amidine salt and (c3) a cyclic quaternary Amidinium salt one, and two or more of them can be used in combination become. Preferred examples include the cyclic amidine (c1).

A cyclic amidine (c1) of the general formula (2) can also be used.


where T ¹ and T ^{2 are} identical or different and each represent a hydrogen atom or a monovalent hydrocarbon radical having 1 to 20 carbon atoms, which is optionally substituted by a hydroxyl group, where T ¹ together with T ² , C and N can form a ring, D represents a divalent hydrocarbon radical having 2 to 10 carbon atoms, which is optionally substituted with an amino group, a nitro group, a cyano group, a carboxyl group, an aldehyde group or a monovalent hydrocarbon radical with 1 to 5 carbon atoms, such as an alkylene radical, an arylene radical and an alkenylene radical ,

Examples of T ¹ and T ² include a methyl group, an ethyl group, an n- or i-propyl group, an n-, i-, tert- or sec-butyl group, a phenyl group, a benzyl group and a hydroxyethyl group.

Examples of D include an ethylene group, a propylene group, a Methylethylene group, an ethenyl group, a methylethenyl group, a Aminoethylene group, a nitroethylene group, a cyanoethylene group, a Carboxyethylene group and a formylethylene group.

Examples of the cyclic amidine (c1) of the above general formula (2) include Compounds with an imidazole ring, a 2-imidazoline ring or a Tetrahydropyrimidine ring as listed below:

(1) Monocyclic imidazole compounds

Imidazole homologues, such as imidazole, 1-methylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1,2-dimethylimidazole, 1-ethyl-2-methylimidazole, 1-phenyl-2-methylimidazole, 1-benzyl-2- methylimidazole, 1-methyl-2-phenylimidazole, 1-methyl-2-benzylimidazole, 1,4- Dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole and 1,4-dimethyl-2- ethylimidazole;

Oxyalkyl derivatives, such as 1-methyl-2-oxymethylimidazole, 1-methyl-2-oxyethylimidazole, 1- Methyl-4-oxymethylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-ethoxymethylimidazole and 1-ethoxymethyl-2-methylimidazole;

Nitro and amino derivatives, such as 1-methyl-4 (5) nitroimidazole, 1,2-dimethyl-4 (5) - nitroimidazole, 1,2-dimethyl-5 (4) aminoimidazole, 1-methyl-4 (5) - (2-aminoethyl) imidazole and 1- (β-aminoethyl) imidazole;

(2) benzimidazole compounds

Benzimidazole, 1-methylbenzimidazole, 1-methyl-2-benzylbenzimidazole, 1-methyl-5 (6) - nitrobenzimidazole and the like;

(3) Compounds with 2-imidazoline ring

2-imidazoline, 1-methylimidazoline, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,4- Dimethyl-2-ethylimidazoline, 1-methyl-2-phenylimidazoline, 1-methyl-2-benzylimidazoline, 1- Methyl-2-oxyethylimidazoline, 1-methyl-2-heptylimidazoline, 1-methyl-2-undecylimidazoline, 1-methyl-2-heptadecylimidazoline, 1- (β-oxyethyl) -2-methylimidazoline, 1-methyl-2- ethoxymethylimidazoline, 1-ethoxymethyl-2-methylimidazoline and the like; and

(4) Compounds with tetrahydropyrimidine ring

Tetrahydropyrimidine, 1-methyl-1,4,5,6-tetrahydropyrimidine, 1,2-dimethyl-1,4,5,6- tetrahydropyrimidine, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5 and other compounds disclosed in Japanese Patent Publication No. S46-37503 (1971) be disclosed.

Preferred examples include the compounds having the imidazole ring, 2-imidazoline ring or tetrahydropyrimidine ring and in particular 1-methylimidazole, 1,2- Dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1-methylbenzimidazole, 1,2- Dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,4-dimethyl-2-ethylimidazoline, 1-methyl 2-heptylimidazoline, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8- Diazabicyclo [5.4.0] undecen-7 and 1,5-diazabicyclo [4.3.0] nonen-5.

Examples of the cyclic tertiary amidine catalyst (c2) include organic salts Acids or salts of inorganic acids of the cyclic amidine (c1).

Examples of the organic acid of the salts of organic acids of the cyclic amidine (c1) include aliphatic monocarboxylic acids such as formic acid, acetic acid, octylic acid and 2- ethylhexanoic acid; aliphatic polycarboxylic acids, such as oxalic acid, malonic acid, Succinic acid, glutaric acid and adipic acid; aromatic monocarboxylic acids, such as Benzoic acid, toluic acid and ethylbenzoic acid; aromatic polycarboxylic acids, such as Phthalic acid, isophthalic acid, terephthalic acid, nitrophthalic acid and trimellitic acid; Phenolic compounds such as phenol and resorcinol; Sulfonic acid compounds, such as Alkylbenzenesulfonic acid, toluenesulfonic acid and benzenesulfonic acid; and Phosphoric acid compounds. Any combination of two or more of the organic Acids can be used. Preferred examples include the aliphatic ones Carboxylic acid compounds and the aromatic carboxylic acid compounds and in particular Octylic acid and formic acid.

Examples of the inorganic acid of the salts of inorganic acids of the cyclic amidine (c1) include hydrochloric acid, sulfuric acid, phosphoric acid, tetrafluoroboric acid, perchloric acid, Hexafluorophosphoric acid, hexafluoroantimonic acid, hexafluoroarsenic acid and Trifluoromethanesulfonic acid. Preferred examples include phosphoric acid.

The cyclic quaternary amidinium salt (c3) generally consists of a cation which by quaternizing the cyclic amidine (c1) as shown above, and an acid anion.

For example, J. Am. Chem. Soc. 69 (1947), 2269 a method for Quaternization of the cyclic amidine (c1) with an alkyl halide as Quaternizing agent. Close examples of another quaternizing agent Dialkyl sulfate, sulfonate ester (U.S.R.S. SU176290), dimethyl carbonate (U.S. Patent No. 2635100), phosphate ester (Journal Prakt. Chemie. Volume 317, Issue 5, 1975, 733) and Compounds containing epoxy group (U.S. Patent No. 2,127,476). If it's necessary, the anionic component of the quaternary compound produced into a special anion transfer to produce the quaternary salt (c3), especially if an organic Anion after quaternization of the cyclic amidine (c1) with the alkyl halide For example, the halide ion, which is produced by quaternization, should be substituted was exchanged for a hydroxide ion and then an organic one Acid are reacted so that the desired quaternary salt with the anion of organic acid.

Preferred examples of the quaternary salt (c3) include the product represented by the Steps reacting the cyclic amidine (c1) with a quaternizing agent with a optionally a hydroxyl group-containing C1 to C11 alkyl or arylalkyl radical and optionally introducing a preferred acid anion is generated by substitution. The product is a salt consisting of a cation with the structure in which the C1 to C11 Alkyl or arylalkyl radical is coupled to a nitrogen atom of the cyclic amidine (c1); and the acid anion.

Examples of the acid that forms the anion in the quaternary salt (c3) include organic or inorganic acids, as listed below:

(1) carboxylic acids

Polycarboxylic acids (dibasic to tetravalent polycarboxylic acids), such as aliphatic Polycarboxylic acids (saturated polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid and itaconic acid); aromatic Polycarboxylic acids. such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic; S-containing polycarboxylic acids, such as thiodipropionic acid;

Oxycarboxylic acids such as aliphatic oxycarboxylic acids such as glycolic acid, lactic acid and Tartaric acid; and aromatic oxycarboxylic acids such as salicylic acid and mandelic acid;

Monocarboxylic acids, such as aliphatic monocarboxylic acids having 1 to 30 carbon atoms (saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, Isobutyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, Lauric acid, myristic acid, stearic acid and behenic acid; unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid and oleic acid); aromatic monocarboxylic acids, such as Benzoic acid, cinnamic acid and naphthoic acid;

(2) phenols

monohydric phenols such as phenol; Alkylphenols, such as cresol, xylenol, ethylphenol, n- or Isopropylphenol, n- or isoamylphenol, isononylphenol and isododecylphenol; Methoxyphenols such as eugenol and guaiacol; naphthol; and cyclohexylphenol;

polyhydric phenols such as pyrocatechol, resorcinol, pyrogallol and phloroglucin;

(3) monoalkyl or dialkyl phosphate esters

Monomethyl or dimethyl phosphate esters, monoisopropyl or diisopropyl phosphate esters, Monobutyl or dibutyl phosphate esters, mono- or di (2-ethylhexyl) phosphate esters and Monoisodecyl or diisodecyl phosphate esters;

(4) sulfonic acids

p-toluenesulfonic acid, dodecylbenzenesulfonic acid and sulfosalicylic acid; and

(5) Inorganic acids

The inorganic acids as listed above.

Preferred examples of the acid include the carboxylic acids and the monoalkyl or Dialkyl phosphate ester and phthalic acid and maleic acid are particularly preferred.

The content of catalyst (C), based on the total weight of the resin (a1) with the active hydrogen atom and the curing agent (a2) with the blocked isocyanate group, is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, particularly preferably 1% by weight or more; preferably 10% by weight or less, more preferably 6% by weight or less, particularly preferably 4% by weight or less. If the Content of catalyst (C) is 0.1 to 10 wt .-%, the resulting can in water dispersed powder slurry coating provide a film with high hardness.

Depending on the desired use, the inventive Slurry coating contain any known additive, such as a setting agent viscoelasticity, a means of adjusting the dynamic surface tension, one Filler, a thickener, a heat resistance or Weather resistance stabilizer, a leveling agent, a defoamer Preservative and a colorant as required.

Examples of the viscoelasticity adjustment agent include adjustment agents the viscoelasticity of the polymer type, such as polycarboxylic acids, polysulfonic acids, with polyether modified carboxylic acids and polyethers; and means for adjusting the viscoelasticity association type, such as urethane modified polyethers. The reactive, surfactant (B) can be used as the reactive agent to adjust viscoelasticity (d1) can be used. The content of agent for adjusting the viscoelasticity, related on the slurry coating is preferably 0.05% to 10.0%, more preferably 0.1% to 5%.

Close examples of the means for adjusting the dynamic surface tension Acetylene glycol agent for adjusting the dynamic surface tension, fluoride agent for adjusting the dynamic surface tension and silicone agent for adjusting the dynamic surface tension. The content of funds for hiring the dynamic surface tension, based on the sludge coating preferably 0.05% to 20.0%, more preferably 0.1% to 10%.

Examples of the weather resistance stabilizer include a UV absorber from Salicylic acid type such as phenyl salicylate and p-tert-butylphenyl salicylate; a UV absorber benzophenone type such as 2,4-dihydroxybenzophenone and 2-hydroxy-4- methoxybenzophenone; a benzotriazole type UV absorber such as 2- (2'-hydroxy-5'- methylphenyl) benzotriazole and 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole; a UV Cyanoacrylate type absorbers such as 2-ethylhexyl-2-cyano-3,3, -diphenyl acrylate; and a hindered amine light stabilizers such as octylated diphenylamine and Isooctyl 3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate. The content of Weather resistance stabilizer, based on the sludge coating preferably 0.05% to 10%, more preferably 0.5% to 3%.

Examples of the leveling agent include olefin resins such as low polyethylene Low molecular weight and low molecular weight polypropylene; olefin copolymers, such as ethylene-acrylic copolymers and ethylene-methacrylic copolymers; (Meth) acrylic copolymers; and polyvinyl pyrrolidone, but are not limited to this. The Leveling agent content, based on the sludge coating, is preferably 0.2% to 6%, more preferably 0.5% to 3%.

Any colorant can be used, including, but not as required limited to an inorganic pigment, an organic pigment and a dye Examples of the inorganic pigment include titanium oxide, carbon black, chromium oxide and ferrite. Examples of the organic pigment include azo pigments such as azo mordants, monoazo Types, diazo types and chelate azo types; and polycyclic pigments such as Benzimidazolone types, phthalocyanine types, quinacridone types, dioxazine types, Isoindolinone types, thioindigo types, perylene types, quinophthalone types and Anthraquinone types, a. Examples of the dye include nigrosine types and aniline Types a. The colorant content, based on the sludge coating, is preferably 0.5% to 30%, more preferably 1.0% to 10%.

Examples of the method for producing the sludge coating according to the invention include, but are not limited to, the following:

(1) Solvent removal method

The reactive, surface-active substance (B) and optionally the non-reactive, surfactant (B ') and the reactive agent for adjusting the viscoelasticity (d1) are contained in an aqueous medium (M) and the resin (a1) and optionally that Hardening agent (a2) and the catalyst (C) are in the organic solvent, such as described above, solved. In another embodiment, the reactive, surfactant (B) and optionally the non-reactive surfactant (B ') and the catalyst (C) contained in the aqueous medium and the resin (a1) and that Hardening agent (a2) and optionally the reactive agent for adjusting the Viscoelasticity (d1) are in the organic solvent, as described above, solved. The solution is immersed in the organic solvent in a reaction vessel Use of a homomixer or the like dispersed in the aqueous medium. While the dispersion is possibly heated up to 100 ° C, it becomes one exposed to reduced pressure of 0.1 to 15 torr, making the water miscible Solvent and the organic solvent are removed, but the water can stay behind. The resulting product is a dispersion comprising water and dispersed the resin particles with an average particle diameter of 0.1 µm to 50 µm in the water.

(2) Powdered particle dispersion method

The resin (a1) and optionally the hardening agent (a2) and the reactive agent for Viscoelasticity adjustments (d1) are melted and kneaded and then cooled and resin particles having an average particle diameter of 0.1 to 50 µm pulverized. In a reaction vessel, the resin particles are in an aqueous medium (M), the reactive, surface-active substance (B) and optionally the non-reactive, contains surfactant (B ') and the catalyst (C) using a Dispersing machine or the like dispersed. In another embodiment the resin (a1) and optionally the curing agent (a2) and the catalyst (C) Resin particles melted and kneaded in an aqueous medium (M) that the reactive, surface-active substance (B) and optionally the non-reactive, surfactant (B ') and the reactive agent for adjusting the viscoelasticity (dl) contains, using a dispersing machine or the like in one Reaction vessel are dispersed.

In the above method (1), the concentration of resin is (a1) and optionally the curing agent (a2) in the organic solvent, preferably 20 to 75% by weight, more preferably 40 to 60% by weight.

In the above process (1) or (2), the concentration of resin is (a1) and optionally the curing agent (a2) in the dispersion, preferably 5 to 70% by weight, more preferably 30 to 60% by weight. The viscosity of the dispersion at 25 ° C preferably 50 to 300,000 mPa.s, more preferably 100 to 10,000 mPa.s, even more preferably 1,000 to 8,000 mPa.s.

In the above method (1), the temperature in the system is preferably -5 to 100 ° C, more preferably 30 to 80 ° C, and the duration of the removal of the solvent is preferably 0.1 to 50 hours, more preferably 2 to 10 hours.

Examples of the dispersing device for the above method include Homomischer, a high pressure homomischer, a dispersing machine, a High pressure homogenizer, a static mixer, a membrane emulsifier, Filmix and an ultrasonic dispersing machine. Preferred examples include the homomixer on.

In the present invention, the reactive surfactant (B) shows good ones Surface activity and good dispersion stability. When the dispersion is applied and is baked, the surfactant can also form a chemical bond to the form dispersed and introduced into the film, so that the film a has excellent water resistance and strength.

The water-dispersed powder sludge coating according to the invention can be found under Use conventional equipment to apply coatings Water based or solvent based coatings can be applied as one Spray coating machine, without need for newly developed equipment.

In one method of producing a film, the slurry coating is applied by means of Spray coating applied to an object so that a wet film thickness of preferably 10 µm to 200 µm, more preferably 10 µm to 100 µm. While the Coating flies from the spray nozzle to the object, the water evaporates from the Coating so that the resin content increases. The resin content (% by weight) of the coating at the time the coating hits the object can be a difference between 100 and a value that is obtained by taking the difference between the applied coating weight and the film weight after Heating divided by the applied coating weight. This salary is preferably 50% to 95% by weight, more preferably 60% to 90% by weight. If the resin content at the time of the coating hit 50% by weight or more is prevented from dripping, and the coating can make a smooth film.

The coated object becomes stronger for a period of preferably 5 to 60 minutes preferably 5 to 30 minutes, particularly preferably 5 to 20 minutes to a temperature of preferably 100 ° C to 200 ° C, more preferably 120 ° C to 180 ° C, so that forms a film.

After application and baking of the coating according to the invention, the resulting film formed on the object preferably has a thickness of 10 µm to 150 µm, more preferably 15 µm to 50 µm.

The content of extract from the film, which after hardening of the invention, in Water-dispersed powder sludge coating, is preferably 10% or less, more preferably 5% or less, still more preferably 1% or less, most preferably 0.1% or less of the extract from the film before the Hardening.

If the value obtained by dividing the extract content from the film after curing by the pre-hardening (hereinafter referred to as "extract content ratio") is 10% or less, the additives can be prevented Remain in the film, wash out (dissolve) in the acid rain and the film deteriorate, and therefore, extract products that are otherwise can be prevented could oxidatively change when the acid rain evaporated and could aggregate which worsens the appearance of the film.

The extract content ratio is a ratio of the extract content by two hours Extraction of the film with ethanol at 78 ° C was obtained to the extract content by extraction for two hours with ethanol at 78 ° C. of a film was obtained before curing, that by applying the water-dispersed according to the invention Powder slurry coating was created.

In the above hardening process, the one dispersed in water Powder sludge coating, for example, on a steel plate treated with zinc phosphate applied by spray coating and prebaked for 10 minutes at preferably 80 ° C and then baked for 20 minutes at preferably 150 ° C and dried.

The water-dispersed powder sludge coating according to the invention is in particular can be used as a top layer for automobiles and when coating building structures, electrical devices and various other products.

EXAMPLES

The present invention is described in more detail, examples below but these examples are not intended to limit the scope of the present invention limit. Hereinafter, the term "part (s)" means "part (s) by weight" and "%" "Wt .-%".

In the examples below, the molecular weight of the reactive, surfactant (B), the resin (a1) with the active hydrogen atom or the Adducts (b3) determined by GPC.

Synthesis example 1

To a reaction vessel that is equipped with a stirrer, a dropping funnel, a nitrogen gas Inlet pipe, a thermometer and a reflux condenser were 53 parts 4-α-cumylphenol and 23 parts of Lewis acid catalyst (GalleonEarth, manufactured by MIZUSAWA INDUSTRIAL CHEMICALS, LTD.). With stirring, the The system's gas space was replaced by nitrogen gas and the materials were opened 90 ° C heated. At the same temperature, 410 parts of product blocked with ethanol from 3-isopropenyl-α, α-dimethylbenzyl isocyanate over a period of 3 hours added dropwise and were able to react for 5 hours at the same temperature. The The reaction mixture was cooled to 30 ° C and then the catalyst was passed through Filtration separated so that 463 parts of adduct of 7 mol of blocked with ethanol Product of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 1 mol of 4-α-cumylphenol were obtained (number average molecular weight 1,900) (B0-1). At 80 ° C 31.1 Parts of adduct of EO and B0-1 (EO content 45%), 66.2 parts of polyethylene glycol (Number average molecular weight 6,000) and 2.6 parts of hexamethylene diisocyanate (hereinafter referred to as HDI) react for 3 hours, which is 100 parts reactive, surfactant (B-1) with an oxyethylene unit content of 66% by weight and a weight average molecular weight of 27,000.

Synthesis example 2

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of EO and the product of the addition reaction of 2 mol styrene and 5 mol a product blocked with ethanol from 3-isopropenyl-α, α-dimethylbenzyl isocyanate 1 mol 4-α-cumylphenol (EO content 10% and number average molecular weight 1,800) was. At 80 ° C., 16.5 parts of the hydrocarbon containing hydroxyl groups, 81.4 parts of polyethylene glycol (number average molecular weight 9,000) and 2.2 parts of TDI 3 hours implemented what 100 parts of reactive surfactant (B-2) with a Oxyethylene unit content of 80% by weight and a weight average molecular weight resulted from 33,000.

Synthesis example 3

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of EO and the product of the addition reaction of 7 mol styrene and 2 mol a product blocked with ethanol from 3-isopropenyl-α, α-dimethylbenzyl isocyanate 1 mol 4-α-cumylphenol (EO content 10% and number average molecular weight 2,000) was. At 80 ° C., 32.1 parts of the hydrocarbon containing hydroxyl groups, 61.6 parts of polyethylene glycol (number average molecular weight 3,000) and 6.8 parts IPDI implemented 3 hours what 100 parts of reactive surfactant (B-3) with an oxyethylene unit content of 60% by weight and a weight average of Molecular weight of 15,000 resulted.

Synthesis example 4

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of EO and the product of the addition reaction of 5 moles of styrene and 1 mole Styrene-p-glycidyl ether with 1 mol phenol (EO content 40% and number average of Molecular weight 1,000). At 80 ° C 10.5 parts of the hydroxyl groups containing hydrocarbon, 87.1 parts of polyethylene glycol (number average of Molecular weight 9,000) and 2.3 parts of HDI implemented for 3 hours, which is 100 parts of reactive, surfactant (B-4) with an oxyethylene unit content of 80% by weight and a weight average molecular weight of 31,000.

Synthesis example 5

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of EO and the product of the addition reaction of 3 mol styrene, 3 mol 3- Isopropenyl-α, α-dimethylbenzyl isocyanate and 2,3-diglycidyloxystyrene with 1 mol of 4-α- Cumylphenol (EO content 5% and number average molecular weight 1,300). at At 80 ° C, 29.4 parts of the hydrocarbon containing hydroxyl groups, 65.1 parts Polyethylene glycol (number average molecular weight 3,000) and 5.5 parts of HDI for 3 hours implemented what 100 parts of reactive surfactant (B-5) with a Oxyethylene unit content of 26% by weight and a weight average molecular weight resulted from 12,000.

Synthesis example 6

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of PO and the product of the addition reaction of 5 mol styrene and 2 mol a product blocked with ethanol from 3-isopropenyl-α, α-dimethylbenzyl isocyanate 1 mol 4-α-cumylphenol (PO content 15% and number average molecular weight 3,200) was. 13.6 was added to 86.4 parts of the hydrocarbon containing hydroxyl groups Parts of sulfuric anhydride are given in such limited quantities that the development of Heat was avoided and was allowed to react at 80 ° C for 3 hours and then neutralized with sodium hydroxide, resulting in 100 parts of reactive, surface-active substance (B-6) with a content of hydrophilic residues of 16 wt .-% and a weight average of Molecular weight of 8,000 resulted.

Synthesis example 7

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of EO and the product of the addition reaction of 7 mol one with Methyl ethyl ketone oxime blocked product from 3-isopropenyl-α, α-dimethylbenzyl isocyanate with 1 mol of phenol (EO content 10% and number average molecular weight 1,800). at At 15 ° C, 52.6 parts of the hydroxyl group-containing hydrocarbon, 65 parts Glacial acetic acid and 52.6 parts of sodium dichromate dihydrate to a carboxylic acid for 5 hours implemented. The resulting carboxylic acid was treated with 44 parts of aminoethyl ethanolamine 12 Hours at 230 ° C implemented what 100 parts of reactive, surface-active substance (B-7) with a content of 27% by weight of hydrophilic residues and a weight average of Molecular weight of 5,800 resulted.

Synthesis example 8

The Friedel-Crafts reaction was carried out in a manner similar to that in Synthesis Example 1 carried out to produce a hydroxyl group-containing hydrocarbon which an adduct of PO and the product of the addition reaction of 5 mol styrene and 2 mol a product blocked with ethanol from 3-isopropenyl-α, α-dimethylbenzyl isocyanate 1 mol of phenol (PO content 15% and number average molecular weight 7,200). To 51.4 Parts of the hydrocarbon containing hydroxyl groups were at 60 ° C over a Period of 1 hour 15.2 parts of acrylonitrile in the presence of 0.5 parts of potassium hydroxide dripped. The reaction mixture was then able to react in 300 parts of methanol, 0.2 Parts of cobalt were used in hydrogen gas at 80 ° C for 6 hours, which is 66.4 parts of a Hydrocarbon containing amino groups (BO-6). After the BO-6, 10.6 Parts of sodium hydroxide and 24.5 parts of methyl chloride into one at 150 ° C. for 6 hours tertiary ammonium could react, the reaction mixture with 73.6 parts of one 30% aqueous solution of sodium monochloroacetate reacted at 70 ° C. for 5 hours, which is 100 parts of reactive surfactant (B-8) containing hydrophilic Residues of 21 wt .-% and a weight average molecular weight of 8,000 resulted.

Comparative Synthesis Example 1

At 80 ° C 19.3 parts of polyoxyalkylene monool (an adduct of ethylene oxide and the Product of the addition reaction of 7 mol styrene with 4-α-cumylphenol, EO content 60% and Number average molecular weight 1,500), 77.4 parts of polyethylene glycol (number average of Molecular weight 6,000) and 3.3 parts of HDI implemented for 3 hours, which is 100 parts surfactant (B'-9) with a hydrophilic residue content of 77 wt .-% and a weight average molecular weight of 18,000.

Production of the hydroxy-functional acrylic resin

250 parts of xylene were added to a reaction vessel and heated to 100.degree. The mixture of the following components (1) to (5) was dropped to the reaction vessel over a period of about 3 hours while the reaction was carried out under a nitrogen atmosphere. After the dropping was finished, the reaction was allowed to proceed for 2 hours while the temperature was kept at 100 ° C. (1) styrene 23 parts (2) methyl methacrylate 23 parts (3) butyl acrylate 20 parts (4) hydroxyethyl acrylate 33 parts (5) Peroxy D (peroxide manufactured by Nippon Oil & Fats Co., Ltd.) 1 parts

After the reaction was completed, the organic solvent and the remaining monomer removed by vacuum distillation. The reaction product was then dried in vacuo using a hydroxy functional acrylic resin (acrylic resin 1) a hydroxyl group equivalent of 420 and a weight average of Molecular weight of 30,000 resulted.

At 100 ° C 59 parts of the resulting acrylic resin 1 and 41 parts of a MEK- Oxime-blocked HDI isocyanurate (DURANATE, manufactured by Asahi Kasei Corporation) kneaded using a heating kneader and then pulverized to about 5 µm, which is a Acrylic resin 2 with an average particle diameter of 7 microns and a Major axes / minor axes ratio of 1.2 resulted.

Manufacture of polyester resin

200 parts of neopentyl glycol, 93 parts of ethylene glycol and Given 355 parts of terephthalic acid, heated to 230 ° C and reacted for 2 hours, the generated water was removed. Then 0.2 part of dibutyltin oxide was added and the reaction could proceed until the acid number became 0.5 or less, so that a Polyester resin with hydroxyl groups at both terminal ends, a weight average of Molecular weight of 14,000 and a hydroxyl number of 16.5 mgKOH / g was obtained (Polyester resin 1).

At 100 ° C, 93 parts of the resulting polyester resin 1 and 7 parts with one MEK oxime blocked HDI isocyanurate (DURANATE, manufactured by Asahi Kasei Corporation) kneaded using a heating kneader and then to about 5 µm pulverized what a polyester resin 2 with an average particle diameter of 7 microns and a major axis / minor axis ratio of 1.2.

Examples of the preparation of a dispersion

In 100 parts of water, 3 parts of each of the reactive surface-active substances (B-1) to (B-8) obtained in Synthesis Examples 1 to 8 of the surface active Substance (B'-9) obtained in Comparative Synthesis Example 1 of the surfactant Low molecular weight substance (B'-10) (an EO adduct of octylphenol, Number average molecular weight 1,000) and PVA (B'-11) (a partially saponified Dispersed polyvinyl alcohol, degree of polymerization 1,700 and degree of saponification 88%), thereby creating a dispersion. The resulting products were each "Dispersion 1" to "Dispersion 11" called.

Examples 1 to 8 and Comparative Examples 1 to 3

59 parts of acrylic resin 1, 41 parts of one with MEK oxime were placed in a beaker blocked HDI isocyanurate (DURANATE, manufactured by Asahi Kasei Corporation) and 100 parts of tetrahydrofuran mixed. The resulting mixture became 100 parts each of dispersions 1 to 11 and then 1 minute at a rate of 9,000 Rpm using an ultradispersion device (manufactured by YAMATO SCIENTIFIC C0., LTD.) Mixed, so that there was an average particle diameter of 5 microns. After this The mixture was mixed into a four-necked flask equipped with a stir bar and a Thermometer was equipped, and then the solvent was at 25 ° C for 10 hours removed under reduced pressure. Subsequently, 0.1 part of a urethane generating catalyst (TEDA, manufactured by Tosoh Corporation), 0.1 part of a Light stabilizers (DIC-TBS, manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED.) And 3.0 parts of a viscoelasticity agent (SN Thickener-651, manufactured by San Nopco Limited.) Added, resulting in a Slurry coating with the average particle diameter and the Major axis / minor axis ratio of the dispersed particle and with each Viscosity as listed in Table 1 was generated.

Examples 9 to 16 and Comparative Examples 4 to 6

100 parts each of the dispersions 1 to 1 l, which in the examples for the preparation of a Dispersion were obtained, 100 parts of fine powder of the hydroxy-functional Acrylic resin (acrylic resin 2) given. The mixture was run at speed for 1 minute of 9,000 rpm using an ultra-disperser (manufactured by YAMATO SCIENTIFIC CO., LTD.) Mixed. Subsequently, 0.1 part of a urethane-producing one Catalyst (TEDA, manufactured by Tosoh Corporation) and 0.1 part of one Light stabilizers (DIC-TBS, manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED.) Added, creating a sludge coating with each average particle diameter and the major axis / minor axis ratio of the dispersed particles and each with the viscosity as listed in Table 2 has been.

Examples 17 to 24 and Comparative Examples 7 to 9

93 parts of polyester resin were placed in a beaker, 1.7 parts with MEK oxime blocked HDI isocyanurate (DURANATE, manufactured by Asahi Kasei Corporation) and 100 parts of tetrahydrofuran mixed. The resulting mixture became 100 parts each of dispersions 1 to 11 and then 1 minute at a rate of 9,000 Rpm using an ultradispersion device (manufactured by YAMATO SCIENTIFIC C0., LTD.) Mixed, so that there was an average particle diameter of 5 microns. After this The mixture was mixed into a four-necked flask equipped with a stir bar and a Thermometer was given, and then the solvent was added for 10 hours 25 ° C removed under reduced pressure. Subsequently, 0.1 part of a urethane generating catalyst (TEDA, manufactured by Tosoh Corporation), 0.1 part of a Light stabilizers (DIC-TBS, manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED.) And 3.0 parts of a viscoelasticity agent (SN Thickener-651, manufactured by San Nopco Limited.) Added, resulting in a Slurry coating with the average particle diameter and the Major axis / minor axis ratio of the dispersed particle and with each Viscosity as listed in Table 3 was generated.

Examples 25 to 32 and Comparative Examples 10 to 12

To 100 parts each of the dispersions 1 to 11, which in the examples for the preparation of a Dispersion were obtained, 100 parts of fine powder of the hydroxy-functional Given polyester resin (polyester resin 2). The mixture was at 1 minute Speed of 9,000 rpm using an ultradispersion device (manufactured by YAMATO SCIENTIFIC CO., LTD.) Mixed. Subsequently, 0.1 part of a urethane generating catalyst (TEDA, manufactured by Tosoh Corporation) and 0.1 part of one Light stabilizers (DIC-TBS, manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED.) Added, creating a sludge coating with each average particle diameter and the major axis / minor axis ratio of the dispersed particles and each with the viscosity as listed in Table 4 has been.

Any sludge coating made using the above procedure was evaluated using the tests described below. The results are in the Tables 1, 2, 3 and 4 listed.

Production of the test piece

The resulting slurry coating was spray coated onto a Zinc phosphate treated steel plate applied and pre-baked at 60 ° C for 10 minutes and then baked at 160 ° C for 10 minutes and dried, resulting in a film with a thickness of 0.03 mm resulted.

evaluation tests Measurement of water resistance

The resulting film was immersed in water at 80 ° C for 120 hours, then slowly cooled to 20 ° C for 3 hours. After wiping the surface of the film with a cloth, the appearance of the film was visually evaluated as follows:
: The appearance of the film is essentially the same before and after immersion.
×: The film shows wrinkling, cracking, blistering or peeling or desquamation.

Measuring the degree of dissolution

The film, which was immersed in water at 25 ° C for 1 hour, became 60 at 1 hour ° C dried and weighed. The resulting weight was compared to the film weight before Immersion was compared and the degree of decrease in film weight was considered Degree of removal determined.

Measurement of film strength

The resulting film was surface hard with a Fischer hardness tester (FISCHERSCOPE® H100 V, manufactured by Fischer Instrumentation (GB) Ltd.) among the Conditions of a load of 0.4 to 100 mN and a notch depth of 5 µm measured. In this test, the hardness of the coating films can be measured with high precision Numbers are transferred and several properties of film strength, such as Notch hardness and Young's modulus of elasticity can be assessed at the same time. The film strength can be assessed by determining the surface hardness.

Dispersibility assessment

The resulting slurry coating was centrifuged at 6,000 rpm in a separator centrifuge for 15 minutes, and then the state of precipitation of the dispersed resin was visually evaluated as follows:
○: The appearance of the dispersed material is essentially the same before and after centrifugation.
Δ: The dispersed material has partially failed due to centrifugation.
×: The dispersed material has completely failed due to centrifugation.

Extract content ratio

After heating and curing, 10 g of the resulting film was extracted with ethanol in a Soxhlet extractor at 78 ° C for 2 hours. The resulting extract content was divided by the extract content of the film before heating and curing to give the ratio.

Synthesis example 9

To a reaction vessel that is equipped with a stirrer, a dropping funnel, a nitrogen gas Inlet pipe, a thermometer and a reflux condenser were 49 parts 4-α-cumylphenol and 6.5 parts of Lewis acid catalyst (GalleonEarth, manufactured by MIZUSAWA INDUSTRIAL CHEMICALS, LTD.). With stirring, the The system's gas space was replaced by nitrogen gas and the materials were opened 90 ° C heated. At the same temperature, 168 parts of product were blocked with ethanol from 3-isopropenyl-α, α-dimethylbenzyl isocyanate over a period of 3 hours added dropwise and were able to react for 5 hours at the same temperature. The The reaction mixture was cooled to 30 ° C and then the catalyst was passed through Filtration separated so that 142 parts of adduct of 3 mol of blocked with ethanol Product of 3-isopropenyl-α, α-dimethylbenzyl isocyanate and 1 mol of 4-α-cumylphenol (Number average molecular weight 2,000). At 80 ° C 189 parts Adduct of EO and product (EO content 25%), 782 parts of polyethylene glycol (number average of molecular weight 9,000) and 29 parts of hexamethylene diisocyanate are reacted for 3 hours, which is 100 parts of reactive surfactant (B-9) with a weight average of Molecular weight of 23,000 resulted.

Examples of the preparation of a dispersion

In 100 parts of water, 3 parts of reactive surfactant (B-9) or surfactant (Orotan 731A, manufactured by Rohm and Haas Company) into one Dispersion dispersed. The resulting products were dispersion 12 "or Called "Dispersion 13".

Example 33

52 parts of acrylic resin 1, 45 parts of one with MEK oxime were placed in a beaker blocked HDI isocyanurate (DURANATE, manufactured by Asahi Kasei Corporation), 3 Parts of 1,8-diazabicyclo [5,4,0] -undecen-7 and 100 parts of tetrahydrofuran mixed. The resulting mixture was added to 100 parts of dispersion 12 and then with for 1 minute a speed of 9,000 rpm using a laboratory mixer (T. K. Robomix, Manufactured by TOKUSHU KIKA KOGYO C0., LTD.) mixed so that there is a medium Particle diameter of 5 microns resulted. After mixing, the mixture was poured into a Four-necked flask equipped with a stir bar and a thermometer, and then the solvent was removed at 25 ° C for 10 hours under reduced pressure. Subsequently, 0.1 part of a light stabilizer (DIC-TBS, manufactured by DAINIPPON INK AND CHEMICALS, INCORPORATED.) And 3.0 parts of one Viscoelasticity Agent (SN Thickener-651 manufactured by San Nopco Limited.) Added, creating a desired, water-dispersed Powder sludge coating with a diameter of the dispersed particles of 5 μm, a major axis / minor axis ratio of 1.0 and a viscosity of 2,000 mPa.s was generated.

Examples 34 to 36 and Comparative Examples 13 to 15

Powder slurry coatings dispersed in water were prepared using the Process prepared from Example 33, except that various dispersions and Catalysts were used as listed in Table 5. Common tertiary Amine catalysts (diazabicyclooctane and diethylethanolamine) were used to in Water-dispersed powder sludge coatings (Comparative Examples 13 and 14) produce. There was also a powder slurry coating dispersed in water without Catalyst (comparative example 15) prepared.

Each of the resulting powder slurry coatings dispersed in water was co-processed the tests described below. The results are shown in Table 5.

Production of the test piece

The test piece was made as described above.

evaluation tests Measurement of the gel percentage

About 10 g of the resulting film was placed in 100 g acetone at 20 ° C for 24 hours immersed and then removed and dried at 60 ° C for 5 hours. The film weight after drying was divided by the film weight before immersion and then by 100 multiplied, which leads to a gel percentage value.

Measurement of film strength

Film strength was measured as described above.

As shown in the previous examples, the invention can be used in water dispersed powder sludge coating of the type hardened at low temperature Provide film with the desired gel content and surface hardness after baking at a temperature of 140 ° C. In contrast, you can the water-dispersed powder sludge coatings from the comparative examples no film with a desired gel content or surface hardness after baking, prepare at 140 ° C and apparently need a high one Baking temperature of 160 ° C to a gel content and a surface hardness on To provide substantially the same level as the present invention.

The powder sludge coating according to the invention dispersed in water can be aground the presence of at least one component from the isocyanate group, the blocked Isocyanate group and the epoxy group in the molecular material and due to the dispersed Resin with the active hydrogen atom has excellent film strength and provide excellent properties of the cured film, such as water resistance. The coating of the invention can have excellent dispersion stability during the Show storage and provide a hardened film that has an extract content ratio of 10% or less and excellent resistance to acid Rain shows.

The powder sludge coating according to the invention dispersed in water from low temperature hardened type can be lower temperature than the conventional one Coating can be burned in and therefore the time required for heating and cooling reduced and productivity improved. The heat source for this lower one Temperature is preferred in terms of the environment.

For example, the powder sludge coating according to the invention is dispersed in water very useful as due to the advantageous effects described above Coating for automobiles, building structures and industrial machines.

Claims (22)

1. A water-dispersed powder slurry coating comprising: (A) a particulate material which (a1) is a resin having an active hydrogen atom includes; (B) a reactive surfactant with at least one Constituent of an optionally blocked isocyanate group and one epoxy group; and (M) an aqueous medium in which the particulate Material and the reactive surfactant are included. 2. A water-dispersed powder slurry coating according to claim 1, further comprising (a2) a curing agent. 3. Water-dispersed powder sludge coating according to claim 1 or 2, wherein the reactive surface-active substance (B) has a hydrophobic unit which an aromatic ring containing hydrocarbon residue of 6 to 100 Carbon atoms; and at least one component from an optionally blocked isocyanate group and an epoxy group. 4. Water-dispersed powder sludge coating according to one of claims 1 to 3, the reactive surface-active substance (B) having a hydrophilic unit, which is selected from at least one constituent from an oxyethylene unit, an anionic residue, a cationic residue and an amphoteric ionic Rest. 5. Water-dispersed powder sludge coating according to claim 3 or 4, wherein the reactive, surface-active substance (B) comprises (L) a urethane resin with at least a component of an optionally blocked isocyanate group and one Epoxy group, and which comprises as main components: (b3) a product of Addition reaction of (b 1) a monohydric phenol or a monohydric aromatic alcohol and at least one component from (b2) a vinyl monomer with an optionally blocked isocyanate group and (b2 ') a vinyl monomer with an epoxy group, or an alkylene oxide adduct of the product of Addition reaction; (b4) an organic diisocyanate; and (b5) at least one Constituent of a diol and a diamine, each with a polyoxyalkylene chain, which includes a polyoxethylene unit. 6. The water-dispersed powder sludge coating according to claim 5, wherein the reactive surfactant (B) comprises at least one compound represented by the general formula (1):


in which
Q is a residue (b3) of a product of an addition reaction of (b1) a monohydric phenol or a monohydric aromatic alcohol and at least one component from (b2) a vinyl monomer with an optionally blocked isocyanate group and (b2 ') a vinyl monomer with an epoxy group, or an alkylene oxide adduct of the product of the addition reaction,
G represents a residue (b4) of an organic diisocyanate, which optionally has a urea bond,
X has the meaning O or NH,
J denotes a radical (b5) of at least one constituent from a diol and a diamine, each of which has a polyoxyalkylene chain which includes a polyoxyethylene unit,
Z represents a hydrogen atom or a radical represented by -COO-Q or -CO-Y,
in which
Y is a residue -OR ¹ ,
in which
R is a monohydric alcohol radical having 1 to 18 carbon atoms or a radical -NR ² R ³ , where
R ^{2 is} a hydrocarbon radical having 1 to 18 carbon atoms or a hydroxyalkyl radical having 1 to 16 carbon atoms, and
R ^{3 represents} a hydrogen atom, a hydrocarbon radical having 1 to 18 carbon atoms or a hydroxyalkyl radical having 1 to 16 carbon atoms, and
m is an integer from 1 to 500. 7. Water-dispersed powder sludge coating according to claim 5 or 6, wherein the vinyl monomer (b2) 3-isopropenyl-α, α-dimethylbenzyl isocyanate, the Isocyanate group is optionally blocked, or 3-ethyleneyl-α, αdimethylbenzyl isocyanate, the isocyanate group being optionally blocked. 8. Water-dispersed powder sludge coating according to one of claims 4 to 7, wherein the reactive surfactant (B) 20 wt .-% to 90 wt .-% Oxyethylene unit contains, based on the weight of the surfactant (B) as a hydrophilic unit. 9. A water-dispersed powder sludge coating according to claim 3 or 4, wherein the reactive surfactant (B) comprises as main components:
(b3 ') a residue of a product of an addition reaction of (b1) a monohydric phenol or a monohydric aromatic alcohol and at least one component from (b2) a vinyl monomer with an optionally blocked isocyanate group and (b2') a vinyl monomer with an epoxy group, or an alkylene adduct of the product of the addition reaction; and
at least one ionic residue, which is selected from an anionic residue, a cationic residue and an amphoteric ionic residue. 10. Water-dispersed powder sludge coating according to one of claims 4 to 9, wherein the reactive surfactant (B) 0.1 wt .-% to 50 wt .-%, based on the weight of the surfactant (B) as a hydrophilic unit, at least an ionic radical which is selected from an anionic radical, a cationic residue and an amphoteric ionic residue. 11. Water-dispersed powder sludge coating according to one of claims 1 to 10, wherein the resin (a1) at least one of an acrylic resin, a polyester resin, a polyurethane resin and an epoxy resin selected component. 12. Water-dispersed powder sludge coating according to one of claims 2 to 11, wherein the curing agent (a2) has a blocked isocyanate group. 13. A water-dispersed powder slurry coating according to claim 12, further comprising (C) at least one catalyst selected from (c1) one cyclic amidine, (c2) a cyclic, tertiary amidine salt and (c3) one cyclic, quaternary amidinium salt. 14. A water-dispersed powder slurry coating according to claim 13, further comprising (B ') a non-reactive surfactant. 15. Water-dispersed powder sludge coating according to claim 13 or 14, wherein the catalyst (C) comprises at least one constituent of cyclic amidines (c1) of the general formula (2):


in which
T ¹ and T ^{2 are} identical or different and each represents a hydrogen atom or a monovalent hydrocarbon radical having 1 to 20 carbon atoms, which is optionally substituted by a hydroxyl group, where T ¹ together with T ² , C and N can form a ring,
D represents a divalent hydrocarbon radical having 2 to 10 carbon atoms, which is optionally substituted with an amino group, a nitro group, a cyano group, a carboxyl group, an aldehyde group or a monovalent hydrocarbon radical with 1 to 5 carbon atoms, and tertiary or quaternary salts thereof. 16. A water-dispersed powder slurry coating according to claim 15, wherein the Catalyst (C) with at least one component from the cyclic amidines (c1) an imidazole ring, a 2-imidazoline ring or a tetrahydropyrimidine ring. 17. Water-dispersed powder sludge coating according to one of claims 2 to 16, further comprising (dl) a reactive, viscoelastic adjusting agent. 18. Water-dispersed powder sludge coating according to one of claims 1 to 17, wherein the particulate material (A) has an average particle diameter of 0.1 µm to 50 µm. 19. Water-dispersed powder sludge coating according to one of claims 1 to 18, wherein the particulate material (A) has a spherical shape with a Major axes / minor axes ratio from 1.0 to 1.5. 20. Water-dispersed powder sludge coating according to one of claims 1 to 19, wherein the particulate material (A) by dispersing in water a solution of the resin (a1) in a solvent and removing the solvent becomes. 21. Film formed by applying the dispersed in water Powder slurry coating according to one of claims 1 to 20 and heating the same. 22. The film of claim 21, wherein the cured film has an extract content ratio of 10% or less, this ratio being the ratio of Extract content, which when extracting the film with ethanol at 78 ° C over two Hours is obtained at the extract content which is when extracting a film before hardening, which is carried out by applying the dispersed in water Powder slurry coating is formed with ethanol at 78 ° C for two hours is obtained.